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CHAPTER 2

CHEMICAL BONDS




2.2 The coulombic attraction is inversely proportional to the distance between
the two oppositely charged ions (Equation 1) so the ions with the shorter
radii will give the greater coulombic attraction. The answer is therefore
(c)
2 2
Mg , O .
+

2.4 The ion is smaller than the Br

ion (196 vs 220 pm). Because the


lattice energy is related to the coulombic attraction between the ions, it
will be inversely proportional to the distance between the ions (see
Equation 2). Hence the larger iodide ion will have the lower lattice energy
for a given cation.

2.6 (a) 7; (b) 10; (c) 7; (d) 2

2.8 (a) [Kr]4d
10
5s
2
5p
6
; (b) [Ar]3d
8
; (c) [Xe]4f
14
5d
3
; (d) [Kr]

2.10 (a) [Ne]; (b) [Kr]4d
3
; (c) [Rn]; (d) [Xe]

2.12 (a) Ca: [Ar]4s
2
, Ti
2+
: [Ar]3d
2
; V
3+
: [Ar]3d
2
In the d block, the energies of
the n-1 d-orbitals lie below those of the ns-orbitals. Therefore, when V and
Ti form ions they lose their 3s electrons before losing their 4d electrons.
(b) Ca: no unpaired electrons; Ti
2+
: two unpaired electrons; V
3+
: two
unpaired electrons. (c) Ti
3+
: [Ar]3d
1
no neutral atom has this electron
configuration.

59
2.14 (a) Au
3+
; (b) Os
3+
; (c) I
3+
; (d) As
3+

2.16 (a) Co
2+
; (b) Rh
2+
; (c) Sn
2+
; (d) Hg
2+

2.18 (a) 3d; (b) 5s; (c) 5p; (d) 4d

2.20 (a) +2; (b) +2 due to the inert pair effect, but 4+ is also possible;
(c) +3; (d) ; (e) 1 2

2.22 (a) 2; (b) 5; (c) 3; (d) 6

2.24 (a) [Ar]3d
10
4s
2
; no unpaired electrons; (b) [Ar]3d
9
; one unpaired
electron; (c) [Xe]5d
10
6s
2
; no unpaired electrons; (d) [Kr]; no unpaired
electrons

2.26 (a) 3d; (b) 6s; (c) 2p; (d) 4p

2.28 (a) +6; (b) (c) [Ne] for +6, [Ar] for 2; 2; (d) Electrons are lost
or added to give noble gas configuration.

2.30 (a) MnTe; (b) Ba
3
As
2
; (c) Si
3
N
4
; (d) Li
3
Bi; (e) ZrCl
4

2.32 (a) FeS; (b) CoCl
3
; (c) Mg
3
P
2

Cl S Cl
..
..
..
..
.
. 2.34
) (b)
.
.
(d) H As H
H
..
Cl Ge Cl
..
..
..
..
.
.
(c)
.
.
Cl
.
.
.
.
..
Cl
..
.
.
.
.
Cl Sn Cl
..
..
..
..
.
.
.
. (a


O N O
..
..
..
..
2.36
) (b)
(d) O Cl
O
..
O O
..
..
.
.
(c)
H C O
..
..
.
.
+
..
..
.
.
.
.
.
.
.
.
..
..
..
.
.
2-
O
.
.
.
.
(a



60
C N
2.38
) (b)
O O
..
..
.
.
(c)
..
..
.
.
2-
.
.
.
.
Zn
2+
2
F B F
..
..
..
..
F
F
.
.
.
.
.
.
.
.
.
.
..
..
.
.
K
+
Ba
2+
(a



2.40
C
N
N N
H
H
H
H
H H
.. ..
+
C
N
N N
H
H
H
H
H H
..
..
+
C
N
N N
H
H
H
H
H H
..
..
+





2.42 No. In order to have resonance structures, only the electrons are allowed to
be rearranged. When atoms are in different relationship to each other, the
result is isomers, not resonance forms.

C
H
H H
+
+1
all H's are 0
Cl O
..
..
.
.
(b)

2.44 )
..
..
.
.
0 -1
(c)
F B F
..
..
..
..
F
F
.
.
.
.
.
.
.
.
.
.
..
..
.
.
0
0
0
0 -1
(a



2.46
0 -1
..
N C N
..
.. ..
2-
-1
lower energy
0 -2
..
N C N
..
2-
0
.
.
.
.
(a)





(b
O A
)
s O
.. ..
..
O
..
O
.
.
.
.
.
.
.
.
.
.
..
..
.
.
-1
-1
-1
-1
+1
3-
O As O
..
..
..
..
O
O
.
.
.
.
.
.
.
.
.
.
..
.
.
-1
0
-1
-1
0
3-
O As O
..
..
..
..
O
O
.
.
.
.
.
.
.
.
0
0
0
0
3-
lower energy
-3






61
(c)
O I O
..
..
..
..
O
O
.
.
.
.
.
.
.
.
..
-1
+1
O I O
..
..
..
..
O
O
.
.
.
.
.
.
.
.
..
.
.
-1
0
+1
-1
0
lowest
0
0
0
0
O I O
..
..
..
..
O
O
.
.
.
.
.
.
.
.
.. -1
+2
O I O
..
..
..
..
O
O
.
.
.
.
.
.
.
.
..
.
.
+3
-1
-1
-1
-1
0
0
.
.
.. -1
-1










2.48 (a) The formal charge distribution is similar for both structures. In the
first, the end nitrogen atom is 1 , the central N atom is +1, and O atom is
0. For the second structure, the end N atom is 0, the central N atom is still
+1, but the O atom is 1 . The second is preferred because it places the
negative formal charge on the most electronegative atom. (b) In the first
structure, there are three O atoms with formal charges of 1 and one O
atom with a formal charge of 0. The formal charge on the P atom is 0. In
the second structure, the P atom has a formal charge of 1 ; there are two
oxygen atoms with formal charges of 1 and two with formal charges of
0. The first structure is preferred because it places the negative formal
charge at the more electronegative atom, in this case O.

2.50 (a) The dihydrogen phosphate ion has one Lewis structure that obeys the
octet rule. Including one double bond to oxygen lowers the formal charge
at P. There are two resonance forms that include this contribution.

.
.
.
.
O P O
O
..
..
.
.
..
..
H O
.
.
.
.
..
H
.
.
.
.
O P O
O
..
..
.
.
..
..
H O
.
.
.
.
H
.
.
.
.
O P O
O
..
.. ..
..
H O
.
.
.
.
..
H




62
(b) There is one Lewis structure that obeys the octet rule shown below at
the left. The formal charge at chlorine can be reduced to 0 by including
one double bond contribution. This gives rise to two expanded octet
structures.

.
.
Cl
O
..
O
.
.
.
.
..
.
.
.
.
.
.
.
.
Cl
O
O
.
.
.
.
..
.
.
.
.
.
.
.
.
Cl
O
..
O
.
.
.
.
.
.
.
.
.
.




(c) As with the two preceding examples, there is one Lewis structure for
the chlorate ion that obeys the octet rule. The formal charge at Cl can be
reduced to 0 by including two double bond contributions, giving rise to
three resonance forms.

.
.
O Cl O
..
..
.
.
..
O
.
.
.
.
..
..
.
.
O
Cl O
..
..
..
O
.
.
.
.
..
O
Cl
O
..
.. ..
O
.
.
.
.
..
..
O Cl
O
..
..
.
.
..
O
.
.
.
.
..
.. .. ..
..





(d) For the nitrate ion, there are three resonance forms that all obey the
octet rule.

.
.
O N O
..
..
.
.
..
O
.
.
.
.
..
.
.
O N
O
..
..
..
O
.
.
.
.
..
O
N O
..
.. ..
O
.
.
.
.
..
..
..
.
.



..
N O
.
..
..
(a) (b)
.
.
F B F
..
..
..
..
.
.
.
.
F
.
.
.
.
..
H C H
H
+
(c)
F
..
.
.
.
.
Br O
.
..
..
(d)
.
.
2.52 The Lewis structures are

Radicals are species with an
unpaired electron, therefore
(a) and (d) are radicals.

63
2.54 (a)



(b)
O Xe O
..
..
..
..
O
.
.
.
.
H C O
H
(c)
O
.
.
.
.
(d)
O O
..
..
.
.
..
..
.
radical
H
..
..
.
O Xe O
..
..
..
O
.
.
.
.
O
.
.
.
.
H
.
.
.
.
radical not a radical
not a radical






2.56 )
(b) (c)
F Cl
..
F
.
.
.
.
F
.
.
.
.
.
.
.
.
Si
..
.
.
..
F
F
F F
F F
(a
..
.
.
..
.
.
.
..
.
.
.
.
.
.
.
..
..
..
..
..
..
12 electrons
2-
I
..
.
.
..
F
F
F F
F F
..
.
.
..
.
.
.
..
.
.
.
.
.
.
.
..
..
..
..
..
..
14 electrons
F
..
..
.
.
..
..
..
.
.
(d)
Br
F
.
.
.
.
F
.
.
.
.
.
.
..
..
.
.
+
10 electrons
8 electrons








(b) (c)
F Cl
..
F
.
.
.
.
.
.
two lone pairs
As
..
.
.
..
F
F
F
F
..
.
.
..
.
.
.
.
.
.
.
.
..
..
F
..
..
.
.
..
..
F
..
..
.
.
.
.
.
.
no lone pairs
S
..
.
.
..
F
F
F
F
..
.
.
..
.
.
.
.
.
.
.
.
..
..
one lone pairs
.
.

2.58
(a)



2.60 Electronegativity decreases with increased mass, so the heavier alkali
metals and alkaline earth metals are the most electropositive. In order of
increasing electropositive character: Li (1.0) < Na (0.93) < K (0.82) ~ Rb
(0.82) < Cs (0.79); Be (1.6) < Mg (1.3) ~ Ca (1.3) < Sr (0.95) < Ba (0.89)
~ Ra (0.9)

64
2.62 Si (1.9) < P (2.2) < S (2.6) ~ C (2.6) < N (3.0) < O (3.4) < F (4.0).
Generally electronegativity increases as one goes from left to right across
the periodic table and as one goes from heavier to lighter elements within
a group.

2.64 (a) The NH bond in NH
3
would be more ionic; the electronegativity
difference between N and H (3.0 versus 2.2) is greater than between P and
H (2.2 versus 2.2). (b) N and O have similar electronegativities (3.0
versus 3.4), leading us to expect that the NO bonds in NO
2
would be
fairly covalent. The electronegativity difference between S and O is
greater, so SO bonds would be expected to be more ionic (2.6 versus
3.4). (c) Difference between SF
6
and IF
5
would be small because S and
I have very similar electronegativities (2.6 versus 2.7). Because I has an
electronegativity closer to that of F, it may be expected that IF
5
would
have more covalent bond character, but probably only slightly more, than
SF
6
.

2.66 : the smaller, more highly charged cations will b
the more polarizing. The ionic radii are 170 pm, 138 pm, 72 pm, and 53
pm, respectively.
2
Cs K Mg Al
+ + +
< < <
3+
e


2.68 : the polarizability should increase as the ion gets
larger and less electronegative.
3 3
N P I At

< < <

2.70 (a)
2 3
NO NO NO

> >
3
NO

. In NO the bond is a double bond, in NO
2
it is the average of a
double and single bond (approximately 1.5), and in
3
NO

it is the average
of three structures in which it is a single bond twice and a double bond
once (approximately 1.33). The nitrate ion would, therefore, be expected
to have the longest NO bond length.
65
(b) C
2
H
2
> C
2
H
4
> C
2
H
6
The bond would be longest in C
2
H
6
in which it is a single bond. In C
2
H
4
it
is a double bond; in C
2
H
2
it is a triple bond.
(c) H
2
CO > CH
3
OH ~ CH
3
OCH
3
All the CO bonds in CH
3
OH and CH
3
OCH
3
are single bonds and would
be expected to be about the same length. The bond in formaldehyde H
2
CO
is a double bond and should be considerably shorter.

2.72 (a) The CO bond in formaldehyde is a double bond, so the expected
bond length will be 67 pm (double bond covalent radius of C) + 60 pm
(double bond covalent radius of O) = 127 pm. The experimental value is
120.9 pm. (b) and (c) The CO bonds in dimethyl ether and methanol
are single bonds. The sum of the covalent single bond radii is 77 + 74 pm
= 151 pm. The experimental value in methanol is 142.7 pm. (d) The
CS bond in methanethiol is a single bond. The sum of the covalent
single bond radii is thus 77 + 102 pm = 179 pm. The experimental value is
181 pm.

2.74 The bond orders as determined by drawing the Lewis structures are 2 for
(a), 1 for (b), and 3 for (c). Therefore, (c) HCN will have the greatest bond
strength.

2.76 The Lewis structures are:

C N
..
..
O
..
..
-2 +1 0
C N
..
O
..
..
-1 +1 -1
.
.
C N
..
O
..
-3 +1 +1
..
.
.
The Lewis structure in the center is probably the most important as it is the
structure with the formal charges of the individual atoms closest to zero.




66

2.78
(a)
C
C
..
C
C
H
H
H
H
H
H
.
.
2-
C
C
C
C
H
H
H
H
H
H
.
.
2-
C
C
..
C
C
H
H
H
H
H
H
.
.
2-
.
.




2.80
P
P
P P
. .
.
.
.
.
.
.



Yes, the molecule obeys the octet rule.

2.82 (a)
C
N
C
N N
C
O O
O
H H
H
C
N
C
N N
C
O O
O
H H
H






(b) (c)










C
N
C
N
C
C
H
O
H
H
H
H
N
H H
C
C
N
N
C
H
H
H
H
67
2.84 Cyclopentadiene has two CC double bonds as shown. There are no
resonance forms possible:

C
C
C C
C
H H
H
H H
H




For the [C
5
H
5
]
-
ion, however, there are five resonance forms possible, as
shown





C
C
C C
C
H
H
H H
H
C
C
C C
C
H
H
H H
H
C
C
C C
C
H
H
H H
H
C
C
C C
C
H
H
H H
H
C
C
C C
C
H
H
H H
H
.
.
.
.
.
.
.
.
.
.
















68
2.86 d(K X) Lattice Energy, kJ/mol
Fluoride 271 826
Chloride 319 717
Iodide 358 645
Lattice Energy vs d(K - X) for KF, KCl and KI
y = -2.0877x + 1389
600
650
700
750
800
850
260 280 300 320 340 360 380
d(K - X), pm
L
a
t
t
i
c
e

E
n
e
r
g
y
,

K
J
/
m
o
l

The data fit a straight line with a correlation coefficient of greater than
99%. (b) From the equation derived for the straight line relationship
Lattice Energy
M X
1.984 1356

= + d
and the value of
K Br
338 pm

= d , we can estimate the lattice energy of KBr


to be 693 .
1
kJ mol

(c) The experimental value for the lattice energy for KBr is 689
, so the agreement is very good.
1
kJ mol


2.88 There are seven resonance structures for the tropyllium cation. All the C
C bonds will have the same bond order, which will be the average of 4
single bonds and 3 double bonds to give 1.43.
69
C
C
C C
C
C
C
H
H
H
H H
H
H
+
C
C
C C
C
C
C
H
H
H
H H
H
H
+
C
C
C C
C
C
C
H
H
H
H H
H
H
+
C
C
C C
C
C
C
H
H
H
H H
H
H
+
C
C
C C
C
C
C
H
H
H
H H
H
H
+
C
C
C C
C
C
C
H
H
H
H H
H
H
+
C
C
C C
C
C
C
H
H
H
H H
H
H +


2.90 The most likely way for these to react is for the molecules to join at the
atoms that possess the unpaired electrons, forming a bond that will pair the
two originally unpaired electrons:
70
O
. .
. .
.
.
+
O
. .
. .
O
. .
. .
O
. .
. .
N O
. .
. .
O
. .
. .
N
. .
.
.
.
.

2.92

Z

Configuration
Number of
unpaired e
-

Element

Charge
Energy
state
38 [Kr]5p
1
1 Sr +1 excited
45 [Kr]4d
7
3 Rh +2 ground
43 [Kr]5s
1
4d
5
6 Tc +1 ground
8 [Ne] 0 O 2 ground
21 [Ar]4s
1
3d
1
2 Sc +1 excited

2.94 (a) C: 1, N: 0; (b) C: 2, N: +1, O: 0; (c) terminal Ns: 1, middle N: +1

2.96 (a) The structure with the lowest formal charges will be the most likely
structure. All of the formal charges on the structure below are zero:

N O N O O

N
+
O
O
O
N
+
O
O
(b)


(c) N
2
O
5
+ H
2
O 2 HNO
3
. The secondary pollutant is nitric acid.

2.98 The energy of the OO bond is given in Table 2.3 as 157 kJ/mol. The
frequency of a photon that would deliver this minimum energy needed to
break the bond is given by:
23 1
14
34
157 kJ/mol 1000 J
1 kJ 6.02214 10 mol
3.39 10 Hz
6.62608 10 J s


= = =

E
h


71
2.100 The CH bond, because the effective mass is lower and the CH bond is
stiffer than the CCl bond.

2.102 This question can be answered by examining the equation that relates the
reduced mass to the vibrational frequency:
1
2
=
k
v
We will assume that the force constant k is essentially the same for the
FeH and FeD bonds and set up the proportionality between the
frequencies of the two vibrations:
1
2
Fe-D Fe-D
Fe-H
1
2
Fe-H

=
k
v
v
k

Fe-H
Fe-D Fe-H
Fe-D
Fe H
Fe H
1 Fe D
Fe D
1
1
1
( )
(1950 cm )
(55.85)(1.01)
55.85 1.01
(55.85)(2.01)
(1950 cm )
55.85 2.01
(1950 cm ) 0.5113
1394 cm

=
+
=
+
+
=
+
=
=
v v
m m
m m
m m
m m

Note that we have also assumed the average mass for Fe to be 55.85
. It would be more correct to use the mass of the particular isotope
of Fe bonded to the H atom. Because that is not given, the average value
has been used. The change in frequency due to the use of different
isotopes of iron is very small compared to the change in frequency due to
the substitution of D for H, because the percentage change in much greater
1
g mol

72
in the latter case. The mass essentially doubles upon replacing H with D;
however, only a small percentage change is observed on going from one
isotope of iron to another.
73